Molecular sieve ssz-71 composition of matter and synthesis thereof

ABSTRACT

The present invention relates to new molecular sieve SSZ-71 prepared using a N-benzyl-1,4-diazabicyclo[2.2.2]octane cation as a structure-directing agent, methods for synthesizing SSZ-71 and processes employing SSZ-71 in a catalyst.

This application claims the benefit under 35 USC 119 of ProvisionalApplication No. 60/639,219, filed Dec. 23, 2004.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new molecular sieve SSZ-71, a methodfor preparing SSZ-71 using a N-benzyl-1,4-diazabicyclo[2.2.2]octanecation as a structure directing agent and the use of SSZ-71 in catalystsfor, e.g., hydrocarbon conversion reactions.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth metal oxides, silica, andalumina. Crystalline borosilicates are usually prepared under similarreaction conditions except that boron is used in place of aluminum. Byvarying the synthesis conditions and the composition of the reactionmixture, different zeolites can often be formed.

SUMMARY OF THE INVENTION

The present invention is directed to a family of molecular sieves withunique properties, referred to herein as “molecular sieve SSZ-71” orsimply “SSZ-71”. Preferably, SSZ-71 is in its silicate, zincosilicate,aluminosilicate, titanosilicate, germanosilicate, vanadosilicate,ferrosilicate or borosilicate form. The term “silicate” refers to amolecular sieve having a high mole ratio of silicon oxide relative toaluminum oxide, preferably a mole ratio greater than 100, includingmolecular sieves comprised entirely of silicon oxide. As used herein,the term “zincosilicate” refers to a molecular sieve containing bothzinc oxide and silicon oxide. The term “aluminosilicate” refers to amolecular sieve containing both aluminum oxide and silicon oxide and theterm “borosilicate” refers to a molecular sieve containing oxides ofboth boron and silicon.

The present invention provides such a molecular sieve having acomposition, as synthesized and in the anhydrous state, in terms of moleratios as follows:

YO₂/WO_(d) 15-∞

M_(2/n)/YO₂ 0-0.03

Q/YO₂ 0.02-0.05

wherein Y is silicon, germanium or a mixture thereof; W is zinc,titanium or mixtures thereof; d is 1 or 2 (i.e., d is 1 when W isdivalent or 2 when W is tetravalent); M is an alkali metal cation,alkaline earth metal cation or mixtures thereof; n is the valence of M(i.e., 1 or 2); and Q is a N-benzyl-1,4-diazabicyclo[2.2.2]octanecation, the as-synthesized molecular sieve having the X-ray diffractionlines of Table I.

In accordance with this invention, there is also provided a molecularsieve produced by the method comprising:

-   -   (1) preparing an as-synthesized molecular sieve having a        composition, as synthesized and in the anhydrous state, in terms        of mole ratios as follows:        -   YO₂/WO_(d) 15-∞        -   M_(2/n)/YO₂ 0-0.03        -   Q/YO₂ 0.02-0.05    -    wherein Y is silicon, germanium or a mixture thereof; W is        zinc, titanium or mixtures thereof; d is 1 or 2 (i.e., d is 1        when W is divalent or 2 when W is tetravalent); M is an alkali        metal cation, alkaline earth metal cation or mixtures thereof; n        is the valence of M (i.e., 1 or 2); and Q is a        N-benzyl-1,4-diazabicyclo[2.2.2]octane cation, the        as-synthesized molecular sieve having the X-ray diffraction        lines of Table 1;    -   (2) thermally treating the as-synthesized molecular sieve at a        temperature (e.g., about 200° C. to about 800° C.) and for a        time sufficient to remove the        N-benzyl-1,4-diazabicyclo[2.2.2]octane cation from the molecular        sieve; and    -   (3) optionally, replacing at least part of the zinc and/or        titanium with a metal selected from the group consisting of        aluminum, gallium, iron, boron, indium, vanadium and mixtures        thereof.

The present invention also includes this thus-prepared molecular sievewhich is predominantly in the hydrogen form, which hydrogen form isprepared by ion exchanging with an acid or with a solution of anammonium salt followed by a second calcination. If the molecular sieveis synthesized with a high enough ratio of SDA cation to sodium ion,calcination alone may be sufficient. For high catalytic activity, theSSZ-71 molecular sieve should be predominantly in its hydrogen ion form.As used herein, “predominantly in the hydrogen form” means that, aftercalcination, at least 80% of the cation sites are occupied by hydrogenions and/or rare earth ions. It should be noted that the mole ratio ofthe first oxide or mixture of first oxides to the second oxide can beinfinity, i.e., there is no second oxide in the molecular sieve. Inthese cases, the molecular sieve is an all-silica molecular sieve or agermanosilicate.

Also provided in accordance with the present invention is a method ofpreparing a molecular sieve comprising (1) a first oxide comprisingsilicon oxide, germanium oxide or a mixture thereof and (2) a secondoxide comprising zinc oxide, titanium oxide or a mixture thereof andhaving a mole ratio of the first oxide to the second oxide of greaterthan about 15 and having, in its as-synthesized, anhydrous state, theX-ray diffraction lines of Table I, said method comprising contactingunder crystallization conditions sources of said oxides and a structuredirecting agent comprising a N-benzyl-1,4-diazabicyclo[2.2.2]octanecation.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a family of molecular sieves designatedherein “molecular sieve SSZ-71” or simply “SSZ-71”. In preparing SSZ-71,a N-benzyl-1,4-diazabicyclo[2.2.2]octane cation (referred to herein as“benzyl DABCO”) is used as a structure directing agent (“SDA”), alsoknown as a crystallization template. The SDA useful for making SSZ-71has the following structure:

The SDA cation is associated with an anion (X—) which may be any anionthat is not detrimental to the formation of the molecular sieve.Representative anions include halogen, e.g., fluoride, chloride, bromideand iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate,and the like. Hydroxide is the most preferred anion.

Benzyl DABCO and a method for making it are disclosed in U.S. Pat. No.5,653,956, issued Aug. 5, 1997 to Zones.

SSZ-71 is prepared from a reaction mixture having the composition shownin Table A below. TABLE A Reaction Mixture Typical PreferredYO₂/WO_(d) >15 >30 OH—/YO₂ 0.10-0.50 0.20-0.30 Q/YO₂ 0.05-0.50 0.10-0.20M_(2/n)/YO₂   0-0.40 0.10-0.25 H₂O/YO₂ 10-80 15-45where Y is silicon, germanium or a mixture thereof; W is zinc, titaniumor mixtures thereof; d is 1 or 2 (i.e., d is 1 when W is divalent or 2when W is tetravalent); M is an alkali metal cation, alkaline earthmetal cation or mixtures thereof; n is the valence of M (i.e., 1 or 2);and Q is a N-benzyl-1,4-diazabicyclo[2.2.2]octane cation.

In practice, SSZ-71 is prepared by a process comprising:

(a) preparing an aqueous solution containing sources of at least oneoxide capable of forming a molecular sieve and a benzyl DABCO cationhaving an anionic counterion which is not detrimental to the formationof SSZ-71;

(b) maintaining the aqueous solution under conditions sufficient to formSSZ-71; and

(c) recovering the SSZ-71.

SSZ-71 can be prepared as a zincosilicate or titanosilicate. However,once the SSZ-71 is made, the zinc and/or titanium can be replaced withother metals by techniques well known in the art. Accordingly, SSZ-71may comprise the molecular sieve and the SDA in combination withmetallic and non-metallic oxides bonded in tetrahedral coordinationthrough shared oxygen atoms to form a cross-linked three dimensionalcrystal structure. The metallic and non-metallic oxides comprise one ora combination of oxides of (1) a first tetravalent element(s), and (2)one or a combination of a divalent element(s), trivalent element(s),pentavalent element(s), second tetravalent element(s) different from thefirst tetravalent element(s) or mixture thereof. The first tetravalentelement(s) is preferably selected from the group consisting of silicon,germanium and combinations thereof. More preferably, the firsttetravalent element is silicon. The divalent element, trivalent element,pentavalent element and second tetravalent element (which is differentfrom the first tetravalent element) is preferably selected from thegroup consisting of zinc, aluminum, gallium, iron, boron, titanium,indium, vanadium and combinations thereof. More preferably, the divalentor trivalent element or second tetravalent element is zinc, aluminum,titanium or boron.

Silicon can be added as silicon oxide or Si(OC₂H₅)₄. Zinc can be addedas a zinc salt such as zinc acetate. Titanium can be added asTi(OC₂H₅)₄.

A source zeolite reagent may provide a source of metals. In most cases,the source zeolite also provides a source of silica. The source zeolitemay also be used as a source of silica, with additional silicon addedusing, for example, the conventional sources listed above. Use of asource zeolite reagent is described in U.S. Pat. No. 5,225,179, issuedJul. 6, 1993 to Nakagawa entitled “Method of Making Molecular Sieves”,the disclosure of which is incorporated herein by reference.

Typically, an alkali metal hydroxide and/or an alkaline earth metalhydroxide, such as the hydroxide of sodium, potassium, lithium, cesium,rubidium, calcium, strontium, barium and magnesium, is used in thereaction mixture; however, this component can be omitted so long as theequivalent basicity is maintained. The SDA may be used to providehydroxide ion. Thus, it may be beneficial to ion exchange, for example,the halide to hydroxide ion, thereby reducing or eliminating the alkalimetal hydroxide quantity required. The alkali metal cation or alkalineearth cation may be part of the as-synthesized material, in order tobalance valence electron charges therein.

The reaction mixture is maintained at an elevated temperature until thecrystals of the SSZ-71 are formed. The hydrothermal crystallization isusually conducted under autogenous pressure, at a temperature between100° C. and 200° C., preferably between 135° C. and 160° C. Thecrystallization period is typically greater than 1 day and preferablyfrom about 3 days to about 20 days.

Optionally, the molecular sieve is prepared using mild stirring oragitation.

During the hydrothermal crystallization step, the SSZ-71 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofSSZ-71 or SSZ-42 (disclosed in U.S. Pat. No. 5,653,956, issued Aug. 5,1997 to Zones) crystals as seed material can be advantageous indecreasing the time necessary for complete crystallization to occur. Inaddition, seeding can lead to an increased purity of the productobtained by promoting the nucleation and/or formation of SSZ-71 over anyundesired phases. When used as seeds, as-synthesized SSZ-71 or SSZ-42crystals (containing the SDA) are added in an amount between 0.1 and 10%of the weight of first tetravalent element oxide, e.g. silica, used inthe reaction mixture.

Once the molecular sieve crystals have formed, the solid product isseparated from the reaction mixture by standard mechanical separationtechniques such as filtration. The crystals are water-washed and thendried, e.g., at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized SSZ-71 crystals. The drying step can be performed atatmospheric pressure or under vacuum.

SSZ-71 as prepared has a mole ratio of an oxide selected from siliconoxide, germanium oxide and mixtures thereof to an oxide selected fromzinc oxide, titanium oxide and mixtures thereof greater than about 15.SSZ-71 further has a composition, as synthesized (i.e., prior tocalcination of the SSZ-71) and in the anhydrous state, in terms of moleratios, shown in Table B below. TABLE B As-Synthesized SSZ-71YO₂/WO_(d) >15 M_(2/n)/YO₂   0-0.03 Q/YO₂ 0.02-0.05where Y, W, d, M, n and Q are as defined above.

SSZ-71 can be made with a mole ratio of YO₂/WO_(d) of ∞, i.e., there isessentially no WO_(d) present in the SSZ-71. In this case, the SSZ-71would be an all-silica material or a germanosilicate. If SSZ-71 isprepared as a zincosilicate, the zinc can be removed and replaced withmetal atoms by techniques known in the art. See, for example, U.S. Pat.No. 6,117,411, issued Sep. 12, 2000 to Takewaki et al. Metals such asaluminum, gallium, iron, boron, titanium, indium, vanadium and mixturesthereof may be added in this manner.

It is believed that SSZ-71 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern.SSZ-71, as-synthesized, has a structure whose X-ray powder diffractionpattern exhibit the characteristic lines shown in Table I and Table IIand is thereby distinguished from other molecular sieves. The XRD datashown in Table I and IA was obtained from a sample of SSZ-71 prepared inthe presence of sodium hydroxide. The XRD data shown in Table II and IIAwas obtained from a sample of SSZ-71 prepared in the presence ofstrontium hydroxide. TABLE I As-Synthesized Zn-SSZ-71 Prepared with NaOH2 Theta^((a)) d-spacing (Angstroms) Relative Intensity^((b)) 5.64 15.7 S8.65 10.2 S 13.65 6.49 M 17.06 5.20 M 20.32 4.37 M 20.64 4.30 VS 23.123.85 M 24.08 3.70 VS 26.15 3.41 M 26.57 3.35 M^((a))±0.15^((b))The X-ray patterns provided are based on a relative intensityscale in which the strongest line in the X-ray pattern is assigned avalue of 100: W(weak) is less than 20; M(medium) is between 20 and 40;S(strong) is between 40 and 60; VS(very strong) is greater than 60.

Table IA below shows the X-ray powder diffraction lines foras-synthesized Zn-SSZ-71 prepared with NaOH including actual relativeintensities. TABLE IA 2 Theta^((a)) d-spacing (Angstroms) RelativeIntensity (%) 5.64 15.7 60 8.65 10.2 57 11.40 7.8 5 11.95 7.4 7 13.116.75 7 13.65 6.49 21 14.34 6.18 5 17.06 5.20 29 17.84 4.97 4 18.23 4.8710 18.84 4.71 12 19.49 4.55 18 20.32 4.37 37 20.64 4.30 100 21.55 4.1216 22.03 4.03 16 23.12 3.85 34 24.08 3.70 62 25.29 3.52 20 25.52 3.49 2026.15 3.41 29 26.57 3.35 33 27.15 3.28 9 28.55 3.13 18 30.00 2.98 830.80 2.90 5 31.68 2.82 10 32.45 2.76 5 33.16 2.70 7 34.92 2.57 11 35.612.52 14 36.90 2.44 12 38.82 2.32 14 40.26 2.24 12^((a))±0.15

TABLE II As-Synthesized Zn-SSZ-71 prepared with Sr(OH)₂ 2 Theta^((a))d-spacing (Angstroms) Relative Intensity^((b)) 5.65 15.6 VS 8.69 10.2 VS16.99 5.22 S 19.52 4.55 M 20.60 4.31 VS 23.13 3.85 M 24.01 3.71 S 24.233.67 M 26.14 3.41 M 26.52 3.36 M^((a))±0.15^((b))The X-ray patterns provided are based on a relative intensityscale in which the strongest line in the X-ray pattern is assigned avalue of 100: W(weak) is less than 20; M(medium) is between 20 and 40;S(strong) is between 40 and 60; VS(very strong) is greater than 60.

Table IIA below shows the X-ray powder diffraction lines foras-synthesized SSZ-71 (Zn-SSZ-71 prepared with Sr(OH)₂) including actualrelative intensities. TABLE IIA 2 Theta^((a)) d-spacing (Angstroms)Relative Intensity (%) 5.65 15.6 84 8.69 10.2 67 11.36 7.8 5 11.94 7.4 513.17 6.7 7 13.68 6.5 20 14.34 6.18 6 15.31 5.79 2 16.99 5.22 42 18.244.86 8 18.79 4.72 17 19.52 4.55 26 20.34 4.37 23 20.60 4.31 100 21.594.12 13 22.06 4.03 16 23.13 3.85 37 24.01 3.71 41 24.23 3.67 25 25.253.53 20 25.52 3.49 23 26.14 3.41 36 26.52 3.36 30 27.10 3.29 12 28.523.13 22 29.85 2.99 6 30.24 2.96 2 30.84 2.90 3 31.64 2.83 11 32.44 2.765 33.11 2.71 5 34.86 2.57 6 35.63 2.52 14 36.10 2.49 6^((a))±0.15

The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ±0.15 degrees.

The X-ray diffraction pattern of Table I is representative of“as-synthesized” or “as-made” SSZ-71 molecular sieves. Minor variationsin the diffraction pattern can result from variations in thesilica-to-zinc or silica-to-titanium mole ratio of the particular sampledue to changes in lattice constants. In addition, sufficiently smallcrystals will affect the shape and intensity of peaks, leading tosignificant peak broadening. The molecular sieve produced by exchangingthe metal or other cations present in the molecular sieve with variousother cations (such as H⁺ or NH₄ ⁺) yields essentially the samediffraction pattern, although again, there may be minor shifts in theinterplanar spacing and variations in the relative intensities of thepeaks. Notwithstanding these minor perturbations, the basic crystallattice remains unchanged by these treatments.

SSZ-71 can be used as-synthesized, but preferably will be thermallytreated (calcined). Usually, it is desirable to remove the alkali metalcation by ion exchange and replace it with hydrogen, ammonium, or anydesired metal ion. The molecular sieve can also be steamed; steaminghelps stabilize the molecular sieve to attack from acids.

The molecular sieve can be used in intimate combination withhydrogenating components, such as tungsten, vanadium, molybdenum,rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such aspalladium or platinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the molecular sieve by replacing someof the cations in the molecular sieve with metal cations via standardion exchange techniques (see, for example, U.S. Pat. No. 3,140,249issued Jul. 7, 1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul.7, 1964 to Plank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964to Plank et al.). Typical replacing cations can include metal cations,e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well astheir mixtures. Of the replacing metallic cations, cations of metalssuch as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, andFe are particularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe SSZ-71. The SSZ-71 can also be impregnated with the metals, or themetals can be physically and intimately admixed with the SSZ-71 usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the syntheticmolecular sieve with a solution containing a salt of the desiredreplacing cation or cations. Although a wide variety of salts can beemployed, chlorides and other halides, acetates, nitrates, and sulfatesare particularly preferred. The molecular sieve is usually calcinedprior to the ion-exchange procedure to remove the organic matter presentin the channels and on the surface, since this results in a moreeffective ion exchange. Representative ion exchange techniques aredisclosed in a wide variety of patents including U.S. Pat. No. 3,140,249issued on Jul. 7, 1964 to Plank et al.; U.S. Pat. No. 3,140,251 issuedon Jul. 7, 1964 to Plank et al.; and U.S. Pat. No. 3,140,253 issued onJul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the molecular sieve is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, themolecular sieve can be calcined in air or inert gas at temperaturesranging from about 200° C. to about 800° C. for periods of time rangingfrom 1 to 48 hours, or more, to produce a catalytically active productespecially useful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of SSZ-71, thespatial arrangement of the atoms which form the basic crystal lattice ofthe molecular sieve remains essentially unchanged.

SSZ-71 can be formed into a wide variety of physical shapes. Generallyspeaking, the molecular sieve can be in the form of a powder, a granule,or a molded product, such as extrudate having a particle size sufficientto pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the SSZ-71 can be extruded beforedrying, or, dried or partially dried and then extruded.

SSZ-71 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

SSZ-71 is useful in catalysts for a variety of hydrocarbon conversionreactions such as hydrocracking, dewaxing, olefin isomerization,alkylation of aromatic compounds and the like.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention.

Examples 1A-1H Synthesis of Zincosilicate SSZ-71 (Zn-SSZ-71)

Zn-SSZ-71 is synthesized by preparing the gels, i.e., reaction mixtures,having the compositions, in terms of mole ratios, shown in the tablebelow. 9.06 g of benzyl DABCO hydroxide (0.815 mmol/g) solution aremixed with 13.8 g of deionized water. Then, respectively, an appropriateamount of ammonium hydroxide or alkali hydroxide or alkaline earthhydroxide is added. Subsequently, 0.18 g of Zn(CH₃COO)₂ are added andstirred at room temperature overnight. Finally, 1.63 g of Cab-O-Sil M-5are mixed and stirred at room temperature for 1 hour. The resulting gelis placed in a Parr bomb reactor and heated in an oven at 150° C. whilerotating at 43 rpm. The reaction is held under these conditions for 17and 29 days, respectively, of run time. Ex. No. Gel Composition Remark1A 0.018(NH₄)₂:0.15R₂O: with NH₄OH only without0.03Zn(CH₃COO)₂:SiO₂:43H₂O AlkOH or AlkE(OH)₂ 1B-1F 0.018Alk₂O:0.15R₂O:Alk = Li, Na, K, Rb or Cs 0.03Zn(CH₃COO)₂:SiO₂:43H₂O (all in hydroxideform) 1G-1H 0.018AlkEO:0.15R₂O: AlkE = Sr or Ba0.03Zn(CH₃COO)₂:SiO₂:43H₂O (all in hydroxide form)R is benzyl DABCO in hydroxide form.Alk is alkali metal.AlkE is alkaline earth metal.

The products are analyzed by X-ray diffraction and determined to beZn-SSZ-71.

Examples 2A-2D Synthesis of Zincosilicate SSZ-71 (Zn-SSZ-71)

Zn-SSZ-71 is synthesized using the procedure of Examples 1A-1H exceptthat EDTA (ethylenediaminetetraacetic acid) is added together with NaOHto the benzyl DABCO hydroxide solution. The reaction is run at 150° C.under rotation at 43 rpm. The gel composition is given below. Ex. No.Gel Composition Synthesis Time, days 2A 0.018Na₂O:0.15R₂O:0.03 EDTA: 70.03Zn(CH₃COO)₂:SiO₂:43H₂O 2B 0.018Na₂O:0.15R₂O:0.03 EDTA: 150.03Zn(CH₃COO)₂:SiO₂:43H₂O 2C 0.018Na₂O:0.15R₂O:0.03 EDTA: 220.03Zn(CH₃COO)₂:SiO₂:43H₂O 2D 0.018Na₂O:0.15R₂O:0.03 EDTA: 290.03Zn(CH₃COO)₂:SiO₂:43H₂OR is benzyl DABCO in hydroxide form.

The products are analyzed by X-ray diffraction and determined to beZn-SSZ-71.

Examples 3A-3B Synthesis of All-Silica SSZ-71 (Si-SSZ-71) UsingBoron-SSZ-42 as Seeds

Si-SSZ-71 is synthesized using the procedure of Example 1A-1H exceptthat (1) no Zn(CH₃COO)₂ is added, (2) 2 wt. % as-made B-SSZ-42 (on theSiO₂ base) is used as seeds and (3) the reaction is run under staticconditions. The gel compositions (excluding the seeds) are given below.The reaction is held under these conditions for 14 days of run time. Ex.No. Gel Composition 3A 0.018(NH₄)₂O:0.15R₂O:SiO₂:43H₂O 3B0.018K₂O:0.15R₂O:SiO₂:43H₂OR is benzyl DABCO in hydroxide form.

The products are analyzed by XRD and found to be Si-SSZ-71.

Examples 4A-4C Synthesis of All-Silica SSZ-71 (Si-SSZ-71) UsingSi-SSZ-71 as Seeds

Si-SSZ-71 is synthesized using the procedure of Examples 3A-3B understatic conditions except that 2 wt. % as-made Si-SSZ-71 (on the SiO₂base) is used as seeds and no ammonium hydroxide or alkali hydroxidesuch as KOH is used. The gel composition (excluding the seeds) is givenbelow. Ex. No. Gel Composition Synthesis Time, days 4A0.15R₂O:SiO₂:43H₂O 2.6 4B 0.15R₂O:SiO₂:43H₂O 28 4C 0.15R₂O:SiO₂:43H₂O 38R is benzyl DABCO in hydroxide form.

The products are analyzed by XRD and found to be Si-SSZ-71 (the productof Example 4A contained SSZ-42 as an impurity).

Examples 5A-5C Synthesis of Si-SSZ-71

Si-SSZ-71 is synthesized as described in Examples 4A-4C under thefollowing conditions:

-   -   (1) with varying amount of water but otherwise identical gel        composition,    -   (2) without NH₄OH or other alkali or alkaline earth hydroxide        (e.g., KOH, etc.),    -   (3) without seeds,    -   (4) under tumbling at 43 rpm,    -   (5) at 150° C.,    -   (6) with two different synthesis time: 15 and 30 days.

The gel compositions and conditions are given below: Tumbled at 43 rpmEx. No. Gel Composition 150° C. 5A (1) 0.15R₂O:SiO₂:43H₂O 15 d 30 d 5B(2) 0.15R₂O:SiO₂:29H₂O 15 d 30 d 5C (3) 0.15R₂O:SiO₂:15H₂O 15 d 30 dR is benzyl DABCO in hydroxide form.

The products are analyzed by XRD and found to be Si-SSZ-71 with theexception of Example 5C at 15 days, which remained a gel.

Examples 6A-6F Synthesis of Titanosilicate SSZ-71 (Ti-SSZ-71)

Ti-SSZ-71 is synthesized by preparing the gels, i.e., reaction mixtures,having the composition, in terms of mole ratios, shown in the tablebelow. Ti(OC₂H₅)₄ and Cab-O-Sil M-5 are used as titanium and siliconsource, respectively. 126.2 g of benzyl DABCO hydroxide (0.614 mmol/g)solution are mixed with 7.3 g of deionized water. Then, 0.61 g ofTi(OC₂H₅)₄ are added under vigorous stirring and then further stirred atroom temperature overnight. Subsequently, an appropriate amount of wateris added to reach the water content given in the gel composition belowbecause some water is evaporated when stirred overnight. Finally, 18.14g of Cab-O-Sil M-5 are mixed and stirred at room temperature for 1 hour.The resulting gel is placed in a Parr bomb reactor and heated in an ovenat 150 or 160° C. while rotating at 43 rpm. Temp, Time, Ex. No. GelComposition ° C. days 6A 0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 150 7 6B0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 150 14 6C0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 150 21 6D0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 160 7 6E0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 160 14 6F0.15R₂O:0.01Ti(OC₂H₅)₄:SiO₂:25H₂O 160 21R is benzyl DABCO in hydroxide form.

The products are analyzed by X-ray diffraction and determined to beTi-SSZ-71.

Examples 7A-7F Synthesis of Titanosilicate SSZ-71 (Ti-SSZ-71)

Ti-SSZ-71 is synthesized by preparing the gels, i.e., reaction mixtures,having the composition, in terms of mole ratios, shown in the tablebelow. Ti(OC₂H₅)₄ and Si(OC₂H₅)₄ are used as titanium and siliconsource, respectively. 39.13 g of Si(OC₂H₅)₄ are placed in a plasticbeaker. 1.30 g of Ti(OC₂H₅)₄ are then quickly added to Si(OC₂H₅)₄ understirring. The mixture of Ti(OC₂H₅)₄ and Si(OC₂H₅)₄ is placed in an icebath. 107.0 g of benzyl DABCO hydroxide (0.614 mmol/g) solution areadded to this mixture under vigorous stirring and then further stirredat room temperature overnight. Subsequently, an appropriate amount ofwater is added to reach the water content given in the gel compositionbelow because some water is evaporated when stirred overnight. Theresulting gel is placed in a Parr bomb reactor and heated in an oven at150 or 160° C. while rotating at 43 rpm. Temp, Time, Ex. No. GelComposition ° C. days 7A 0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 160 7 7B0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 160 14 7C0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 160 21 7D0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 150 7 7E0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 150 14 7F0.175R₂O:0.03Ti(OC₂H₅)₄:SiO₂:28H₂O 150 21R is benzyl DABCO in hydroxide form.

The products are analyzed by X-ray diffraction and determined to beTi-SSZ-71.

Examples 8A-8C Synthesis of Titanosilicate SSZ-71 (Ti-SSZ-71)

Si-SSZ-71 is synthesized as described in Examples 7A-7F except that 2wt. % as-made Si-SSZ-71 (on the SiO₂ base) is used as seeds. The gelcomposition (excluding the seeds) is given below. Ti(OC₂H₅)₄ andSi(OC₂H₅)₄ are used as titanium and silicon source, respectively. Theresulting gel is placed in a Parr bomb reactor and heated in an oven at150° C. while rotating at 43 rpm. Temp, Time, Ex. No. Gel Composition °C. days 8A 0.175R₂O:0.01Ti(OC₂H₅)₄:SiO₂:28H₂O 150 6 8B0.175R₂O:0.01Ti(OC₂H₅)₄:SiO₂:28H₂O 150 18 8C0.175R₂O:0.01Ti(OC₂H₅)₄:SiO₂:28H₂O 150 24R is benzyl DABCO in hydroxide form.

The products are analyzed by X-ray diffraction and determined to beTi-SSZ-71.

Example 9 Calcination of ZN-SSZ-71

Na/Zn-SSZ-71 as synthesized in Example 1C with NaOH is calcined toremove the structure directing agent (SDA) as described below. A thinbed of Na/Zn-SSZ-71 in a calcination dish is heated in a muffle furnacefrom room temperature to 120° C. at a rate of 1° C./minute and held for2 hours. Then, the temperature is ramped up to 540° C. at a rate of 1°C./minute and held for 5 hours. The temperature is ramped up again at1C/minute to 595° C. and held there for 5 hours. A 50/50 mixture of airand nitrogen passes through the muffle furnace at a rate of 20 standardcubic feet (0.57 standard cubic meters) per minute during thecalcination process.

Example 10 Conversion of calcined Zn-SSZ-71 to Al-SSZ-71

The calcined Na/Zn-SSZ-71 (5 g) prepared in Example 9 is with combinedwith 500 grams of 1 M aqueous Al(NO₃)₃ solution and treated under refluxfor 100 hours. The resulting Al-SSZ-71 product is then washed with 1liter of water, filtered and air-dried at room temperature in vacuumfilter.

Example 11

The Al-SSZ-71 material prepared in Example 10 is loaded with 1.0 wt.-%Pt via impregnation with aqueous Pt(NH₃)₄(NO₃)₂ solution and tested withbifunctionally catalyzed hydrocracking of FCC LCO (light cycle oil). TheFCC LCO is first hydrotreated over a Ni/Mo hydrotreating catalyst at660° F. and 1700 psig to reduce its sulfur and nitrogen contents. Thehydrotreated LCO is then hydrocracked over Pt/AI-SSZ-71 at 750° F. and1000 psig. The results from the simulated distillation via GC analysisare given below. Temperature, ° F. Hydrotreated LCO Hydrocracked VolumePercent Untreated over Ni/Mo LCO over Pt/Al- Intervals, % LCO catalystSSZ-71 5 393 382 273 10 436 417 322 15 453 437 366 20 477 455 395 25 491467 413 30 502 481 433 35 520 495 445 40 534 508 457 45 546 522 471 50562 535 484 55 577 548 497 60 593 563 513 65 609 576 529 70 623 592 54275 637 608 560 80 652 625 576 85 670 643 599 90 689 666 623 95 716 699660

1. A molecular sieve having a composition, as synthesized and in theanhydrous state, in terms of mole ratios as follows: YO₂/WO_(d) 15-∞M_(2/n)/YO₂ 0-0.03 Q/YO₂ 0.02-0.05 wherein Y is silicon, germanium or amixture thereof; W is zinc, titanium or mixtures thereof; d is 1 or 2; Mis an alkali metal cation, alkaline earth metal cation or mixturesthereof; n is the valence of M; and Q is aN-benzyl-1,4-diazabicyclo[2.2.2]octane cation, the as-synthesizedmolecular sieve having the X-ray diffraction lines of Table I.
 2. Amolecular sieve according to claim 1 wherein Y is silicon.
 3. Amolecular sieve according to claim 1 wherein W is titanium and Y issilicon.
 4. A molecular sieve according to claim 1 wherein W is zinc andY is silicon.
 5. A molecular sieve produced by the method comprising:(1) preparing an as-synthesized molecular sieve having a composition, assynthesized and in the anhydrous state, in terms of mole ratios asfollows: YO₂/WO_(d) 15-∞ M_(2/n)/YO₂ 0-0.03 Q/YO₂ 0.02-0.05  wherein Yis silicon, germanium or a mixture thereof; W is zinc, titanium ormixtures thereof; d is 1 or 2 (i.e., d is 1 when W is divalent or 2 whenW is tetravalent); M is an alkali metal cation, alkaline earth metalcation or mixtures thereof; n is the valence of M (i.e., 1 or 2); and Qis a N-benzyl-1,4-diazabicyclo[2.2.2]octane cation, the as-synthesizedmolecular sieve having the X-ray diffraction lines of Table 1; (2)thermally treating the as-synthesized molecular sieve at a temperatureand for a time sufficient to remove theN-benzyl-1,4-diazabicyclo[2.2.2]octane cation from the molecular sieve;and (3) optionally, replacing at least part of the zinc and/or titaniumwith a metal selected from the group consisting of aluminum, gallium,iron, boron, indium, vanadium and mixtures thereof.
 6. A molecular sieveaccording to claim 5 wherein Y is silicon.
 7. A molecular sieveaccording to claim 5 wherein Y is silicon and W is zinc.
 8. A molecularsieve according to claim 5 wherein Y is silicon and W is titanium.
 9. Amolecular sieve according to claim 5 wherein Y is silicon and the zincand/or titanium is replaced with boron.
 10. A molecular sieve accordingto claim 5 wherein Y is silicon and the zinc and/or titanium is replacedwith aluminum.
 11. A molecular sieve according to claim 5 wherein saidmolecular sieve is predominantly in the hydrogen form.
 12. A molecularsieve according to claim 5 wherein said molecular sieve is substantiallyfree of acidity.
 13. A method of preparing a molecular sieve comprising(1) a first oxide comprising silicon oxide, germanium oxide or a mixturethereof and (2) a second oxide comprising zinc oxide, titanium oxide ora mixture thereof and having mole ratio of the first oxide to the secondoxide of greater than 15 and having, in its as-synthesized, anhydrousstate, the X-ray diffraction lines of Table I, said method comprisingcontacting under crystallization conditions sources of said oxides and astructure directing agent comprising aN-benzyl-1,4-diazabicyclo[2.2.2]octane cation.
 14. The method accordingto claim 13 wherein the first oxide is silicon oxide.
 15. The methodaccording to claim 13 wherein the second oxide is zinc oxide.
 16. Themethod according to claim 13 wherein the second oxide is titanium oxide.17. The method according to claim 13 wherein the molecular sieve isprepared from a reaction mixture comprising, in term of mole ratios:YO₂/WO_(d) >15 OH-/YO₂ 0.10-0.50 Q/YO₂ 0.05-0.50 M_(2/n)/YO₂ 0-0.40H₂O/YO₂ 10-80 wherein Y is silicon, germanium or a mixture thereof; W iszinc, titanium or mixtures thereof; d is 1 or 2; M is an alkali metalcation, alkaline earth metal cation or mixtures thereof; n is thevalence of M; and Q is a N-benzyl-1,4-diazabicyclo[2.2.2]octane cation.